Preparation of gamma-butyrolactones

ABSTRACT

Gamma-butyrolactones are formed by reacting an olefin with a compound containing a carboxylate moiety having at least one hydrogen atom on the alpha carbon atom in the presence of an ion of manganese, cerium, or vanadium, the ion being in a valency state higher than its lowest valency state.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a continuation-in-part of copending application Ser.No. 336,857 filed Feb. 28, 1973, now U.S. Pat. No. 4,175,089 issued Nov.20, 1979 which in turn is a continuation-in-part of copendingapplication Ser. No. 30,582, filed Apr. 21, 1970, now abandoned. Thelatter application is a continuation-in-part of application Ser. No.714,447, filed Mar. 20, 1968, which application was pending at the timeapplication Ser. No. 30,582 was filed but which has since beenabandoned.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to a process for the production ofgamma-butyrolactones.

2. Description of the Prior Art

U.S. Pat. No. 2,569,064 discloses the preparation of gamma lactones byheating a 2,2,4-trihalogenoalkanoic ester in the presence of a catalyticamount of a metal halide including zinc chloride, boron trifluoride,antimony pentachloride, stannic chloride, and ferric chloride.

U.S. Pat. No. 2,968,568 discloses the preparation of butyrolactones byreacting bromoacetic acid and derivatives of the carboxylic groupthereof with alpha olefins and with a catalyst. Catalysts which producefree radicals under the reaction conditions and polymerization catalystsare preferred. Catalysts disclosed are peroxides such as cumenehydroperoxide, acetyl peroxide, propionyl peroxide, lauroyl peroxide,benzoyl peroxide, benzoyl hydroperoxide and hydrogen peroxide. Othercatalysts include perborates, percarbonates, persulfates,tetraethyllead, hydrazines, substituted hydrazines and their salts, andamine oxides such as triethyl amine oxide. Other means for producingfree radicals which can be employed include ultraviolet light with orwithout chemical photosensitizers.

SUMMARY OF THE INVENTION

Gamma-butyrolactones are produced by reacting an olefin with a compoundcontaining a carboxylate moiety having at least one carbon atom on thealpha carbon atom in the presence of an ion of manganese, cerium, orvanadium, the ion being in a valency state higher than its lowestvalency state.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

The reaction between an olefin with a compound containing a carboxylatemoiety having at least one carbon atom on the alpha carbon atom in thepresence of an ion of manganese, cerium, or vanadium in a valency statehigher than the lowest valency state to produce a butyrolactone isexemplified in the following equation form using ethylene as the olefin,acetic acid as the compound containing the carboxylate moiety having atleast one carbon atom on the alpha carbon atom, and manganese in itstrivalent state: ##STR1##

In equation (4), the alpha (α), beta (β), and gamma (γ) carbon atoms ofthe gamma-butyrolactone product are labeled. The overall reaction is:##STR2## showing that one mole of ethylene in the presence of themanganic ion (Mn⁺⁺⁺) gives one mole of lactone.

As shown in equation (1), the acetic acid reacts with a stoichiometricamount of the manganic ion, Mn⁺⁺⁺, to form the carboxymethyl freeradical, (A), a hydrogen ion, H⁺, and manganous ion, Mn⁺⁺. According tothe reaction of equation (2), which takes place in the presence of theethylene reactant and the products of equation (1), the carboxymethylfree radical, (A), adds to the double bond of the ethylene forming thefree radical, (B). The free radical, (B), then reacts with manganic ionto form the cation, (C), and manganous ion, as shown in equation (3). Asshown in equation (4), the cation, (C), cyclizes to form thegamma-butyrolactone product, (P), and a hydrogen ion, H⁺.

From the foregoing, it will be appreciated that the substituents on thealpha carbon atom of the gamma-butyrolactone product are thesubstituents on the alpha carbon atom of the carboxylic acid, the alphacarbon atom on the carboxylic acid being the carbon atom adjacent to thecarboxy group, ##STR3## and the substituents on the beta and gammacarbon atoms of the gamma-butyrolactone product are the substituents onthe carbon atoms joined by the double bond of the olefin.

Various olefins may be employed in the preparation of thegamma-butyrolactones by the process of the invention. These olefins maybe monoolefins or diolefins and may be acyclic monoolefins or diolefinsand cyclic monoolefins or diolefins. The diolefins may be conjugated ornon-conjugated. The acyclic monoolefins may be straight chain orbranched chain monoolefins and may contain between 2 and 200 carbonatoms. Preferably, however, the acylic monoolefins contain between 2 and92 carbon atoms and, still more preferably, contain between 2 and 10carbon atoms. The acyclic diolefins may contain between 3 and 8 carbonatoms. The cyclic monoolefins may contain between 5 and 8 carbon atomsand the cyclic diolefins may also contain between 5 and 8 carbon atoms.The acyclic monoolefins may contain one or more aromatic groups,preferably phenyl groups. Further, the acyclic monoolefins may containchlorine or bromine substituents or a carboxy or carboxymethylsubstituent.

Suitable illustrative olefins include ethylene, propylene, the butenes,pentenes, hexenes, heptenes, octenes, nonenes, and decenes. Otheracyclic monoolefins which may be employed are olefin oligomers such aspropylene and isobutylene tetramer, isobutylene trimer, and propylenepentamer and hexamer. Other suitable illustrative olefins includeallene, butadiene, pentadiene, isoprene, biallyl, heptadiene, andbimethallyl. Still other suitable illustrative olefins includecyclopentene, cyclohexene, cycloheptene, cyclooctene, cyclopentadiene,cyclohexadiene, cycloheptadiene, and cyclooctadiene. Acyclic monoolefinscontaining one or more aromatic groups include styrene, methyl styrene,stilbene, 1,1-diphenyl ethylene, and methyl cinnamate. Representativeolefins containing chlorine, bromine, carboxy or carboxymethylsubstituents include bromostyrene, methyl cinnamate, methylacrylate,dimethyl maleate, polychloroethylene, oleic acid and methyl oleate.

It will be seen that the foregoing olefins are those of the formula##STR4## wherein one or more of the Rs are hydrogen, straight orbranched chain alkyl groups, the total number of carbon atoms in thealkyl groups being between 1 and 198, an alkenyl group containing 1 to 6carbon atoms, a phenyl group, a phenyl group or an alkyl group of nomore than 7 carbon atoms each containing a chlorine, bromine, carboxy orcarboxymethyl substituent, and, where one R is other than hydrogen, itmay be joined to each of the carbon atoms of the double bond.

A particular group of olefins useful in this invention is that class inwhich one of the foregoing Rs is a substituted alkenyl group. Inparticular, the class is described by the generic formula ##STR5##wherein --X₁ and --X₂ are substituents each individually selected fromthe group consisting of --Cl (chloro), --Br (bromo), --CN (cyano),--COOAlk (carboxyalkyl wherein Alk is an alkyl group with up to sixcarbon atoms and preferably is a methyl or ethyl group), and --COCH₃(acetyl). These compounds all may be regarded as4-methyl-1,3-pentadienes. The gamma butyrolactones formed from thesepentadienes by reaction of one of the double bonds are useful as highboiling solvents for coatings. As chemical intermediates, the lactonesmay be converted to lactams and used as selective solvents forextraction of aromatic hydrocarbons or as monomers for the preparationof polyamide resins. A particularly useful lactone having the structure##STR6## wherein --X₁ and --X₂ are as hereinabove described may beisolated and converted to pyrethroid-like compounds having insecticidalactivity. In the structure just described --X₃ may be hydrogen for thecase in which the foregoing pentadiene is reacted with acetic acid; butbroadly, --X₃ may be selected from the group consisting of hydrogen,--CH₃ (methyl), --C₂ H₅ (ethyl), --CN (cyano), and --COOH (carboxyl),said substituent deriving from acetic or substituted acetic acid havingthe generic formula ##STR7## In the foregoing description of --X₃, it isto be understood that when the substituted acetic acid is malonic acidthe esters thereof also may be used, especially the monomethyl ester.

The conversion of the foregoing lactone structure to a pyrethroid-likecompound is conducted by synthetic methods well known to those skilledin the art and need not be detailed here since they do not constitutepart of this invention. However, by way of background, such conversionfor the pentadiene wherein both --X₁ and --X₂ are chloro was describedby Dr. R. A. Raphael in San Francisco on Aug. 28, 1976 at the NationalMeeting of the American Chemical Society. This conversion is alsodisclosed in a publication by Alfred Bader in Aldrachimeca Acta, Vol. 9,No. 3 pages 49-51 (1976), the entire contents of which is hereinincorporated by reference.

The pentadienes contemplated as particularly suited to produce theabove-described pyrethroid-precursor lactone are those having thestructure ##STR8## wherein both --X₁ and --X₂ are --Cl; or wherein --X₁is --COOCH₃ or --COOC₂ H₅ and --X₂ is --CH₃ ; or wherein --X₁ is --COCH₃and --X₂ is --CH₃ ; or wherein both --X₁ and --X₂ are --Br; or whereinX₁ is --CN and --X₂ is --CH₃ ; or wherein --X₁ is --COOCH₃ or --COOC₂ H₅and --X₂ is --COCH₃ ; or wherein both --X₁ and --X₂ are --CN; or wherein--X₁ is --COOCH₃ or --COOC₂ H₅ and --X₂ is --Cl or --Br.

The carboxylic acid employed in the preparation of thegamma-butyrolactones by the process of the invention must, as indicatedin the foregoing equations (1) to (4), contain at least one hydrogensubstituent on the alpha carbon atom. The other substituents includehydrogen, saturated or unsaturated alkyl groups containing 1 to 10carbon atoms, cyano, and alkyl carboxy or alkyl carboxymethyl groups.The alkyl carboxy or alkyl carboxymethyl groups may contain 1 to 6carbon atoms in the alkyl portion thereof.

Suitable illustrative carboxylic acids include acetic, propanoic, thebutanoic, the pentanoic, the hexanoic, the heptanoic, the octanoic, thenonanoic, the decanoic, the undecanoic, and the dodecanoic acids. Othersuitable illustrative carboxylic acids include the butenoic, pentenoic,hexenoic, heptenoic and dodecanoic acids. Still other suitableillustrative carboxylic acids include cyanoacetic, succinic, glutaric,adipic, pimelic, suberic, and azelaic acids and their mono-methylesters.

It will be seen that the foregoing acids are those of the formula##STR9## wherein one or both of the R's are hydrogen, a straight orbranched chain alkyl or alkenyl group containing 1 to 10 carbon atoms, acyano, or an alkyl carboxy ##STR10## or alkyl carboxymethyl ##STR11##group where the alkyl group contains 1 to 6 carbon atoms, i.e., n=1-6.

As will be apparent, some of the olefins named above can contain carboxygroups having at least one hydrogen atom on the alpha carbon atom andsome of the acids named above may contain an olefinic group. Theseolefins and acids therefore can act either as an olefin or acid. If anolefinic acid is reacted with an olefin, the olefinic acid will react asan acid and if reacted with an acid, the olefinic acid will react as anolefin. If two olefinic acids are reacted, a portion of the amount ofeach in the reaction mixture will act as an olefin and the remainder asan acid.

The reaction for the production of the gamma-butyrolactones is carriedout, as stated, in the presence of an ion of manganese, cerium, orvanadium. The ion of manganese, cerium, or vanadium must be in a valencystate higher than its lowest valency state. Manganese can exist in fivevalency states, namely, in valency states of 2, 3, 4, 6, and 7. Ceriumcan exist in two valency states, namely, in valency states of 3 and 4.Vanadium can exist in three valency states, namely, in valency states of2, 3, and 5. Thus, in carrying out the reaction, the ion of manganesemust be in a valency state of 3, 4, 6, or 7, the ion of cerium must bein a valency state of 4, and the ion of vanadium must be in a valencystate of 3 or 5.

The preferred ion for the gamma-butyrolactone producing reaction istrivalent manganese, i.e., manganese ion in a valency state of 3 orMn⁺³. As indicated in the foregoing equations (1) to (5), the trivalentmanganese ion is reduced during the reaction to bivalent manganese,i.e., manganese in a valency state of 2 or Mn⁺². The trivalentmanganese, or manganic ion, may be provided in the gamma-butyrolactoneproducing reaction mixture by including therein manganic acetatedihydrate. This compound may be formed by refluxing an acetic acidsolution of manganous acetate, i.e., acetate where the valency state ofthe manganese is 2, or Mn⁺², with potassium permanganate. Other suitablemanganic ion-producing compounds or mixtures for providing manganic ioninclude (1) anhydrous manganic acetate, (2) a mixture of activated(i.e., freshly prepared or acid treated) manganese dioxide and aceticacid, (3) a mixture of manganese sesquioxide and acetic acid, and (4) amixture of manganic manganous oxide (Mn₃ O₄) and acetic acid. Themanganic ion may also be provided by including in the reaction mixturemanganic chloride, manganic fluoride, manganic hypophosphate dihydrate,manganic sulfate, manganic phosphate monohydrate, or manganicpyrophosphate.

The manganese ion in higher valent form may also be provided bymanganese ion in a valency state higher than 3. For example, themanganese ion may be in a valency state of 4, 6, or 7. Manganese in avalency state of 4 may be obtained from a mixture of manganese dioxide(MnO₂) and acetic acid. The manganese ion in a valency state of 6 may beprovided by the manganate of sodium, potassium, ammonium, lithium,magnesium, strontium, calcium, or barium. The manganese ion in a valencystate of 7 may be provided by the permanganate of sodium, potassium,ammonium, or magnesium.

In addition to the foregoing, the manganese ion in a higher valencystate may be provided by mixtures of manganese ions. Such mixturesinclude those of manganous ion, Mn⁺², plus any manganese ions having avalency state of 3, 4, 6, or 7. The manganic manganous oxide mentionedabove is a mixture of manganese ions in the valency states of 2 and 3.

The compound chosen to provide the manganese ion in the higher valencystate should have solubility, preferably complete solubility in thegamma-butyrolactone producing reaction mixture.

The cerium ion of higher valency state may be provided in the reactionmixture for producing the gamma-butyrolactone by including therein cericacetate. This compound may be formed by reacting a ceric salt soluble inacetic acid with acetic acid. Such salts include ceric ammonium nitrate,ceric nitrate, and ceric sulfate. Alternatively, the cerium ion ofhigher valency state may be provided in the reaction mixture forproducing the gamma-butyrolactone by including therein a ceric salt,other than the acetate, soluble in the reaction mixture. Such cericsalts soluble in the reaction mixture include those mentioned above.

The vanadium ion of higher valency state may be provided in the reactionmixture for producing the gamma-butyrolactone by including thereinvanadic (V⁺² or V⁺⁵) acetate. This compound may be formed by reacting avanadic salt soluble in acetic acid with acetic acid. Such salts includevanadium trichloride, vanadium tribromide, vanadium trifluoridetrihydrate, vanadium tetrafluoride and ammonium metavanadate.Alternatively, the vanadium ion of higher valency state may be providedin the reaction mixture for producing the gamma-butyrolactone byincluding therein a vanadic salt, other than the acetate, soluble in thereaction mixture. Such vanadic salts soluble in the reaction mixtureinclude those mentioned above.

The compound providing the ion of manganese, cerium, or vanadium in avalency state higher than its lowest valency state may be added per seto the reaction mixture or, if desired, it may be formed in situ. Insitu formation may suitably be accomplished by adding to the reactionmixture, for example, a manganous compound like manganous acetatetogether with a solvent therefor like acetic acid and also adding anoxidizing agent so that the manganous ion is oxidized to at least tomanganic ion, Mn⁺⁺⁺. Suitable oxidizing agents include nitric acid,chlorine, oxygen, air, ozone, various peroxides like peracetic acid andhydrogen peroxide, or intermediate peroxides or hydroperoxides, such astertiary butyl hydroperoxide, resulting from the air oxidation ofhydrocarbons. Electrochemical oxidation is a suitable oxidizingprocedure. Where an oxidizing agent is added to the reaction mixture,the oxidizing agent can oxidize the olefin and, in this case, the ion ofmanganese, cerium, or vanadium in its lower valency state is maintainedin high concentration in the reaction mixture in order to effectoxidation of the ion preferentially to that of the olefin.

The reaction mixture for the production of the gamma-butyrolactones mayalso contain a solvent. The use of a solvent is indicated where any ofthe reactants are not otherwise soluble in the reaction mixture underthe reaction conditions. Any solvent inert with respect to the reactantsunder the reaction conditions and which will remain in the liquid stateunder the reaction conditions may be employed. A suitable solvent is asaturated hydrocarbon such as hexane and higher alkanes having up to 30carbon atoms. Ethers may also be employed as a solvent.

A carboxylic acid may also be employed as a solvent. However, where acarboxylic acid other than the carboxylic acid desired for reaction withthe olefin to produce the gamma-butyrolactone is employed as a solvent,the solvent carboxylic acid will compete with the reactant carboxylicacid to produce gamma-butyrolactone. The extent to which the solventcarboxylic acid will compete with the reactant carboxylic acid willdepend upon the relative reactivities of the two acids and the relativeproportions of each in the reaction mixture. Thus, where thereactivities of the two acids, as measured by their disassociationconstants, are substantially similar, the extent of competition willdepend primarily upon the relative proportions, from a molar standpoint,of the two acids in the reaction mixture. The reaction product in thisinstance will be a mixture of gamma-butyrolactone derived from thereactant carboxylic acid and gamma-butyrolactone derived from thesolvent carboxylic acid, the relative proportions of thegamma-butyrolactones depending upon the relative proportions of theacids in the reaction mixture. On the other hand, where the reactivitiesof the two acids are substantially dissimilar, the more reactive acidwill compete with the less reactive acid to the practical exclusion ofthe less reactive acid regardless of the relative proportions of each inthe reaction mixture. However, where the acids have equivalentreactivities, such as acetic and propionic acids, it is convenient toadd the ion to the reaction mixture as the salt of the acetic acid whileusing the propionic acid as the solvent and the lactone product will bethat of the propionic acid.

Carboxylic acids which may be employed as solvents may be straight orbranched chain. Included among these acids are acetic acid, propionicacid and the butanoic and pentanoic acids. Acid anhydrides may also beused as solvents. Water or paraffinic hydrocarbons may be used inconjunction with carboxylic acid solvents. Dimethyl acetamide may beemployed as a solvent.

Considering now the conduct of the reaction, the ratio of the olefin inthe reaction mixture may be from 0.01 to 3 moles, preferably 0.25 to 1mole per mole of ion of manganese, cerium, or vanadium. The carboxylicacid is preferably in an amount to provide at least one mole per mole ofolefin. The solvent, if employed, will be present in an amountsufficient to dissolve a portion of the reactants. The reaction iscarried out by subjecting the reactants to a temperature between 20° C.and 250° C., preferably between 50° C. and 180° C. The rate of reactionwill, of course, depend upon the temperature employed and will alsodepend upon the activity of the carboxylic acid. With the more reactivecarboxylic acids, such as cyanoacetic acid, lower temperatures may beemployed with satisfactorily rapid rates of reaction. Refluxing may beemployed. The reaction may be carried out under pressure, if necessary,to maintain a liquid phase. The reaction time may extend from one hourto 10 hours. An inert atmosphere, such as one of nitrogen, carbondioxide, helium, or the like, is desirably maintained over the reactionmixture to lessen or avoid oxidation by air. Where the olefin employedreadily polymerizes, it is preferred to add it slowly to the remainderof the reaction mixture to minimize polymerization.

At the conclusion of the reaction, separation of the lactone product maybe effected by conventional distillation, fractional crystallization,extraction, and the like with or without the aid of conventionalfiltration or centrifugation. For example, in a reaction mixturecontaining lactone product from acetic acid and ethylene, manganousacetate, and any unreacted ethylene, the mixture may be filtered toremove any solids and then subjected to distillation, using vacuum ifnecessary. The lactone has a higher boiling point than the acetic acidand the acetic acid, and any of the normally gaseous ethylene that maybe remaining in the reaction mixture, will distill off leaving thelactone product.

High yields of lactone are obtainable by the process of the invention.Up to 95%, or more, of the olefin may be converted to lactone indicatingthat the carboxylic acid has selectivity to addition to the double bondof the olefin in the presence of the ion of manganese, cerium, orvanadium. Without restricting the invention to the theoreticalconsiderations, it is believed that, owing to the use of the ion ofmanganese, cerium, or vanadium, the selectivity is a result of therelatively fast oxidation of the free radical (B) (note the foregoingequation (3)) to the cation (C). Where manganic ion is employed, about 1mole of lactone may be formed per 2 moles of manganic ion reduced and,as shown in the examples following, lactone yields of about 50% to about85% based on the manganic ion reduced are obtainable. On the basis ofolefin consumed, the yields are higher. The addition of a potassiumsalt, or other alkali metal salt of the carboxylic acid, may help tosuppress formation of minor side products. It also increases the boilingpoint of the reaction mixture and thereby permits the use of highertemperatures to facilitate reaction without the use of pressure.

The lactone product depends on the starting olefin and on the carboxylicacid. Thus, with ethylene as the starting olefin, and using acetic acidand manganic acetate dissolved in acetic acid, the product is a simplelactone like gamma-butyrolactone, ##STR12## where the alpha, beta, andgamma carbons are substituted only by hydrogen. As the starting olefinbecomes more complex, so too the lactone product becomes complex, asindicated in Examples 1-8, where lactones with beta and/or gammasubstituents are shown. These products may be named on the basis of theformula just given; thus the product of Example 1 isbetamethyl-gamma-phenyl-butyrolactone; that of Example 2 is gamma,gamma-methyl-phenyl-butryolactone, etc. With propionic acid and manganicacetate dissolved in propionic acid, and using ethylene as the startingolefin, the resulting lactone is alphamethyl-butyrolactone, ##STR13##and as is apparent, has a methyl substituent in the alpha position. Anindication of additional products is given below.

The manganous compound that is formed as a consequence of the reductionof the manganic compound may, as already indicated, be saved and used toregenerate the manganic compound. Thus, where the manganous compound ismanganous acetate, it is desirably isolated from the reaction mixture,heated at 200°-300° C. to form MnO, acetone, and carbon dioxide, and theoxide then heated in air or oxygen to form MnO₂, Mn₂ O₃, and/or Mn₃ O₄.On dissolving these oxides in acetic acid, there is formed manganicacetate, and this solution is of use to prepare a lactone in accordancewith equations (2) and (3) above. The acetone, of course, is valuableenough to recover.

Alternatively, the isolated manganous acetate may be dissolved in aceticacid and the solution electrolyzed, using a carbon or other suitableanode, to form manganic acetate, the resulting electrolyzed solutionbeing directly usable in a lactone-forming reaction. Where the manganousacetate is already in solution in acetic acid, no preliminary isolationstep is necessary as such solution may be charged to the electrolysiscell and electrolyzed.

Or the isolated manganous acetate may be dissolved in water, thesolution buffered to pH 6 to 8 by means of ammonium chloride or othersuitable buffer, and air or oxygen passed through the solution toproduce manganese sesquioxide. This oxide is filtered and dissolved inacetic acid to form a solution of manganic acetate.

The isolated manganous acetate may also be treated with an oxidizingagent like concentrated or fuming nitric acid plus acetic anhydride toproduce anhydrous manganic acetate, which is useful per se in thelactone-forming reaction.

As a further alternative, the manganous acetate, either isolated or inacetic acid solution, may be mixed with acetic acid and with activatedMnO₂ to form manganic acetate. To obtain activated MnO₂, one can freshlyprepare this oxide, or can treat an existing sample with a dilutemineral acid following this with water washing and drying.

Manganous acetate can also be oxidized to manganic acetate by treatmentwith potassium permanganate.

The foregoing regeneration procedures generally apply to other manganouscompounds besides the acetate; and with suitable modifications they areapplicable to the regeneration of the other higher-valent compounds ofcerium and vanadium from lower-valent forms thereof. It will beappreciated that the regeneration step permits the manganese, cerium, orvanadium compound to be used over and over and therefore represents asignificant economy.

Whereas the invention has been described herein specifically inconnection with a carboxylic acid having at least one hydrocarbon atomon the alpha carbon atom as the compound containing a carboxylate moietyhaving at least one hydrogen atom on the alpha carbon atom, it is to beunderstood that other compounds may also provide the necessarycarboxylate moiety. Thus, the necessary carboxylate moiety may beprovided by a manganese, cerium, or vanadium carboxylate having at leastone hydrogen atom on the alpha carbon atom, the metal being in a valencystate higher than its lowest valency state, where a solvent other than acarboxylic acid having at least one carbon atom on the alpha carbonatom, such as dimethyl acetamide is employed. In this instance, takingmanganic acetate as an example, the reaction proceeds as follows:

    Mn(OCOCH.sub.3).sub.3 →CH.sub.2 COOH+Mn(OCOCH.sub.3).sub.2 ( 5),

to produce the free radical (A) as in the foregoing equation (1). Thereaction proceeds subsequently as indicated in the foregoing equations(2)-(4), the Mn⁺⁺⁺ ion in equation (3) being provided by the manganicacetate. The necessary carboxylate moiety may also be provided by theanhydride of a carboxylic acid having at least one hydrogen atom on thealpha carbon atom. Thus, taking acetic anhydride and taking Mn₂ O₃ asthe compound providing the ion of manganese, cerium, or vanadium in avalency state higher than its lowest valency state, the reactionproceeds as follows: ##STR14## and the manganic acetate produces thefree radical (A) as in the foregoing equation (5), the reactionproceeding subsequently as indicated in the foregoing equations (2)-(4),the Mn⁺⁺⁺ ion in equation (3) being provided by the manganic acetate.The necessary carboxylate moiety may also be provided by a salt ofmanganese, cerium, or vanadium other than a carboxylate, the manganese,cerium, or vanadium being in a valency state higher than its lowestvalency state, in the presence of a carboxylate other than that ofmanganese, cerium, or vanadium, the carboxylate having at least onehydrogen atom on the alpha carbon atom. Thus, taking manganic chlorideas the salt of manganese, cerium, or vanadium and potassium acetate asthe carboxylate, the reaction proceeds as follows:

    MnCl.sub.3 +3CH.sub.3 COOK→Mn(OCOCH.sub.3).sub.3 +3KCl (7),

the manganic acetate producing the free radical (A) as in equation (5)and the reaction proceeding subsequently as indicated in the foregoingequations (2)-(4), the Mn⁺⁺⁺ ion in equation (3) being provided by themanganic acetate.

The following examples illustrate the preparation of lactones fromseveral olefins at different reaction conditions and by use of varioussources of reducible metal ions.

EXAMPLES 1-8

In separate procedures, each of the olefins listed in the table belowwas dissolved in glacial acetic acid to form a solution ranging from0.05 to 1 molar with respect to the olefin. To such solution there wereadded 2 mole equivalents of manganic acetate, Mn(C₂ H₃ O₂)₃.2H₂ O andabout 300 grams per liter of anhydrous potassium acetate, the latterbeing employed to suppress any undesired side products. The resultingsolution was then heated to refluxing under a nitrogen atmosphere untilthe brown manganic color disappeared, this step requiring from 0.5 to 6hours, depending on the olefin. Thereafter the reaction mixture wasanalyzed for lactone content by means of vapor phase chromatography. Thefollowing table shows the lactone formed from each starting olefin,together with the yield, the latter being calculated on the basis ofMn⁺³ consumed. No attempt was made to optimize the yield, although itmay be noted that the yields are higher when based on the consumedolefin.

                                      TABLE I                                     __________________________________________________________________________    EXAMPLE                                                                       NO.    OLEFIN      LACTONE      YIELD %                                       __________________________________________________________________________    1      trans-beta-methylstyrene                                                                   ##STR15##   79                                            2      a-methylstyrene                                                                            ##STR16##   74                                            3      octene-1                                                                                   ##STR17##   74                                            4      trans-octene-4                                                                             ##STR18##   56                                            5      cyclooctene                                                                                ##STR19##   65                                            6      trans-stilbene                                                                             ##STR20##   --                                            7      styrene                                                                                    ##STR21##   --                                            8      cis-beta-methylstyrene                                                                     ##STR22##   79                                            __________________________________________________________________________     .sup.(a) Only one isomer was obtained (presumably the trans).                 .sup.(b) Two isomers in the ratio of 5:1 were obtained.                  

EXAMPLES 9-17

In each of these examples, the operations described in Examples 1-8 wererepeated employing the olefins listed in Table II below. The table alsolists the lactones obtained. In each case, the yield of the lactone wasbetween 50-75% based on the Mn⁺³ consumed.

                  TABLE II                                                        ______________________________________                                        EX.                                                                           NO.   OLEFIN         LACTONE                                                  ______________________________________                                         9    1,1-diphenylethylene                                                                         gamma-diphenyl butyrolactone                             10    cis-octene-4   beta-n-propyl-gamma-n-propyl                                                  butyrolactone                                            11    2-methylheptene-1                                                                            gamma-methyl-gamma-n-pentyl                                                   butyrolactone                                            12    p-methylstyrene                                                                              gamma-p-methylphenyl                                                          butyrolactone                                            13    p-bromostyrene gamma-p-bromophenyl                                                           butyrolactone                                            14    m-bromostyrene gamma-m-bromophenyl                                                           butyrolactone                                            15    decene-1       gamma-n-octyl butyrolactone                              16    dodecene-1     gamma-n-decyl butyrolactone                              17    hexadecene-1   gamma-n-tetradecyl                                                            butyrolactone                                            ______________________________________                                    

EXAMPLES 18-25

In each of the following examples, the olefin, listed in Table III, wasemployed. In each example, to a 1.3 liter pyrex bomb were added 29.24grams (0.1 mole) of manganic acetate dihydrate and 950 milliliters of a10% solution of potassium acetate in acetic acid. The mixture wasdegassed by bubbling nitrogen through it for a period of 20 minutes. Themanganic acetate dihydrate dissolved upon warming the mixture to 50° C.Then, in rapid succession 34.03 grams (0.4 mole) of cyano-acetic acidand 0.200 mole of the olefin were added. These were rinsed into the bombwith 50 milliliters of acetic acid. After one hour at 50° C., the aceticacid was distilled from the mixture using a rotovap. The residue wastaken up in 1500 milliliters of water and extracted with 400, 300, and200 milliliter-portions of diethyl ether. The combined ether layers werethen extracted with sufficient cold 10% aqueous solution of sodiumcarbonate to form a slightly basic aqueous layer. The basic layer wasthen extracted once with diethyl ether. The combined ether layers weredried over anhydrous magnesium sulfate, filtered, and evaporated to aconstant weight. Table III lists the lactone obtained, and the yield,for each of the olefins.

                                      TABLE III                                   __________________________________________________________________________    EXAMPLE                                                                       NO.    OLEFIN       LACTONE      YIELD %                                      __________________________________________________________________________    18     octene-1     alpha-cyano-gamma-n-                                                                       60                                                               hexyl butyrolactone                                       19     styrene      alpha-cyano-gamma-                                                                         41                                                               phenyl butyrolactone                                      20     alpha-methylstyrene                                                                        alpha-cyano-gamma-                                                                         43                                                               methyl-gamma-phenyl                                                           butyrolactone                                             21     cis-beta-methylstyrene                                                                     alpha-cyano-beta-                                                                          50                                                               methyl-gamma-phenyl                                                           butyrolactone                                             22     trans-beta-methylstyrene                                                                   alpha-cyano-beta-                                                                          50                                                               methyl-gamma-phenyl                                                           butyrolactone                                             23     octene-4     alpha-cyano-beta,                                                                          49                                                               gamma-di-n-propyl                                                             butyrolactone                                             24     isoprene                  44                                                   ##STR23##                                                             25     2,5-dimethylhexadiene-1,5                                                                   ##STR24##   20                                           __________________________________________________________________________     .sup.(a) The ratio of the major isomer to the minor product was 8:1.     

EXAMPLES 26-37

In each of these examples, a different olefin was employed. About 0.015mole of the olefin and 8.1 gram (0.03 mole) of manganic acetatedihydrate were added to 73 milliliters of glacial acetic acid containing10% of potassium acetate. The mixture was then sealed in a glass tubeand heating in an oil bath at temperatures between 140° C. and 180° C.When the characteristic brown color due to manganic ion had disappeared,the reaction was stopped and the reaction mixture extracted with diethylether and water. Table IV lists the olefin, the lactone obtained, andthe yield.

                                      TABLE IV                                    __________________________________________________________________________    EXAMPLE                                                                       NO.    OLEFIN       LACTONE             YIELD %                               __________________________________________________________________________    26     isobutylene  gamma-dimethyl      30                                                        butyrolactone                                             27     3-methylbutene-1                                                                           gamma-iso-propyl    50                                                        butyrolactone                                             28     methylcinnamate                                                                             ##STR25##          45                                    29     methylacrylate                                                                              ##STR26##          --                                    30     dimethylmaleate                                                                             ##STR27##          --                                    31     hexadiene-1,5                                                                               ##STR28##          25                                    32     octadiene-1,7                                                                               ##STR29##          26                                    33     2,5-dimethylhexadiene-1,5                                                                   ##STR30##          --                                    34     butadiene    gamma-vinyl         30                                                        butyrolactone                                             35     isoprene                                                                                    ##STR31##          50                                    36     cyclopentadiene                                                                             ##STR32##          --                                    37     cyclohexadiene-1,3                                                                          ##STR33##          --                                    __________________________________________________________________________

EXAMPLE 38

Styrene in an amount of 2.1 grams and 11.65 grams of manganic acetate,Mn(C₂ H₃ O₂)₃.2H₂ O, comprising two equivalents of Mn⁺³ based ontitration value, were refluxed under nitrogen in 200 milliliters ofpropionic acid containing 20 grams of potassium propionate. In less thanan hour, a 50% yield of alpha-methyl-gamma-phenyl butyrolactone wasobtained.

EXAMPLE 39

The procedure of Example 38 was repeated except that isobutyric acid wasused in place of propionic acid and sodium isobutyrate was used in placeof potassium propionate. The lactone obtained wasalpha-dimethyl-gamma-phenyl butyrolactone.

EXAMPLE 40

To a mixture of 700 grams of succinic acid and 300 milliliters of aceticacid at reflux were added 14.1 grams of monosodium succinate, 40 gramsof potassium acetate, and 12 grams of octene-1. Manganic acetatedihydrate in the amount of 27 grams (0.1 mole) was added over a periodof 15 minutes. When the brown color had disappeared, three more grams ofoctene-1 and 27 more grams of manganic acetate dihydrate were added.When the reaction was completed, the mixture was diluted with water andextracted with ether. The reaction product obtained in 25% yield wascrystallized from petroleum ether and melted at 76°-76.5° C. This wasidentified as the lactone shown below by analytical and spectral means:##STR34##

EXAMPLE 41

Manganese acetate tetrahydrate (Mn(OAc)₂.4H₂ O) in the amount of 860grams (3.5 moles) was added to 6 liters of acetic acid. The mixture washeated to 116° C. with nitrogen purge. Potassium permanganate in theamount of 132 grams (0.84 mole) was added slowly over 1/2 hour. Thetypical brown color of Mn⁺³ ion appeared immediately upon addition. Thesolution was stirred at about 100° C. for 1/2 hour, and potassiumacetate in the amount of 1800 grams was then added in 600-gramincrements. The reaction temperature was increased by taking solvent offin a Dean Stark side arm. After 1 liter of solvent was taken off, 200milliliters of decene-1 were added to the reaction mixture. The mixturewas then kept at reflux until the brown Mn⁺³ color disappeared. Thereaction mixture was then cooled down and 1 liter of ice water wasadded. The resulting mixture was extracted 4 times with 1 literincrements of benzene. The benzene was stripped, leaving a residue of224 grams of product which analyzed for 88% pure gamma-n-octylbutyrolactone. The yield was 47.5% based upon the Mn⁺³ ion.

EXAMPLE 42

Octene-1 in an amount of 2.2 grams and 23.6 grams of ceric acetate wererefluxed under nitrogen in 200 milliliters of glacial acetic acidcontaining 60 grams of potassium acetate for less than 0.4 hour, therebeing obtained a 31% yield of gamma-n-hexyl butyrolactone.

EXAMPLE 43

Styrene in the amount of 20 grams was dissolved in 100 milliliters ofacetic acid containing 10% potassium acetate. Ceric acetate in theamount of 0.005 mole was added and the reaction mixture was heated in asealed tube at 110° C. overnight. The lactone, gamma-phenylbutyrolactone, was obtained in 70% yield.

EXAMPLE 44

The procedure of Example 43 was repeated, except that propionic acid andsodium propionate were used in place of acetic acid and potassiumacetate. Alpha-methyl-gamma-phenyl butyrolactone was obtained in 60%yield.

EXAMPLE 45

The procedure of Example 43 was repeated except that isobutyric acid andsodium isobutyrate were employed in place of acetic acid and potassiumacetate. The lactone obtained was alpha-dimethyl-gamma-phenylbutyrolactone.

EXAMPLE 46

Ammonium meta-vanadate in the amount of 0.01 mole (1.17 grams) was addedto 100 milliliters of acetic acid containing 0.02 mole (2.24 grams) ofoctene-1 in an ampoule. This solution was purged with nitrogen. Theampoule was sealed and placed in a 145° C. bath. The color of thesolution went from deep yellow to dark blue. After 2.5 hours, the samplewas cooled and worked up by diluting with ether and washing the etherwith ice water and cold aqueous saturated sodium bicarbonate. The etherextract was dried with sodium sulfate and stripped on a rotovap. Thisgave a major product identified as ##STR35##

EXAMPLE 47

Ammonium meta-vanadate in the amount of 0.01 mole (1.17 grams) was addedto 100 milliliters of 10% potassium acetate in acetic acid. The reactionmixture was heated to reflux with nitrogen purge. Octene-1 in the amountof 0.02 mole (2.24 grams) was added, followed by 0.04 mole (3.4 grams)of cyano acetic acid. The solution immediately turned from yellow todark blue. The solution was refluxed for 15 minutes, cooled, and workedup by diluting with ether and washing the ether with ice water and coldsaturated aqueous sodium bicarbonate. The ether extract was dried withsodium sulfate and the solvent stripped off on a rotovap. The majorproduct obtained was identified as ##STR36##

EXAMPLE 48

About 1.69 g. (0.015 mole) octene-1 and 8.1 g. (0.03 mole) manganicacetate were added to 73 ml. glacial acetic acid and the mixture sealedin a tube. No potassium acetate was used. The tube was placed in an oilbath maintained at 138° C., and after 4 hours the characteristic darkbrown color due to manganic ion disappeared. The reaction was stoppedand the reaction mixture worked up by extracting with ether and water.Gamma-n-hexyl-butyrolactone was obtained in a yield of 2.0 g.,comprising 78% of theory.

EXAMPLE 49

About 1.69 g. octene-1 and 7.0 g. anhydrous manganic acetate were addedto 150 ml. glacial acetic acid containing 45 g. potassium acetate andthe mixture refluxed under nitrogen. The reaction was complete in lessthan two hours, and gamma-n-hexyl-butyrolactone was recovered in 65%yield.

EXAMPLE 50

Octene-1 in an amount of 3.37 g. and 4.8 g. of freshly prepared MnO₂.4H₂O were mixed with and heated under nitrogen in 300 ml. glacial aceticacid containing 90 g. potassium acetate. After a reaction time of lessthan two hours, gamma-n-hexyl-butyrolactone was obtained in 74% yield.

EXAMPLE 51

Octene-1 in an amount of 2.24 g. and 5.1 g. of Mn₂ O₃ (comprising twoequivalents of Mn⁺³ based on titration value) were refluxed undernitrogen in 200 ml. glacial acetic acid containing 60 g. potassiumacetate. After a period of less than two hours,gamma-n-hexyl-butyrolactone was obtained in a yield of 61%.

EXAMPLE 52

Octene-1 in an amount of 2.2 g. and 23.6 g. of ceric ammonium nitrate,Ce(NH₄)₂ (NO₃)₆, were refluxed under nitrogen in 200 ml. glacial aceticacid containing 60 g. potassium acetate for less than 0.5 hour, therebeing obtained a 48% yield of gamma-n-hexyl-butyrolactone.

EXAMPLE 53

Octene-1 in an amount of 2.24 g. and 11.65 g. of manganic acetate, Mn(C₂H₃ O₂)₃. 2H₂ O, (comprising two equivalents of Mn⁺³ based on titrationvalue), were refluxed under nitrogen in 200 ml. propionic acidcontaining 20 g. potassium propionate. In less than an hour a good yieldof alphamethyl-gamma-n-hexyl-butyrolactone was obtained.

EXAMPLE 54

The work of Example 52 was repeated, except that styrene was used inplace of octene-1. The product was gamma-phenyl-butyrolactone.

EXAMPLE 55

The work of Example 53 was repeated, with the same results, except that3.2 g. of freshly prepared MnO₂ were used in place of the manganicacetate.

EXAMPLE 56

Potassium permanganate in the amount of 15.8 grams was added at 40° C.to 92 grams manganous acetate, Mn(OCOCH₃)₂, in acetic acid. To theresulting solution were added 94 grams of polybutene-1 having amolecular weight of 800, i.e., containing 64 carbon atoms, and themixture was refluxed under nitrogen for 4 hours. The lactone product wasextracted from the reaction mixture with hexane and was obtained in 55%yield based on infra-red and acid determination value.

EXAMPLE 57

A stock solution was prepared by heating at 115° C. 500 milliliters ofacetic acid, 150 grams of potassium acetate, and 245 grams of manganousacetate tetrahydrate, Mn(OCOCH₃)₂.4H₂ O. A 50-milliliter aliquot of thestock solution was added to 2 milliliters of a 0.312 molar solution oftertiary butyl hydroperoxide in acetic acid. The solution also contained400 microliters of octene-1. After heating, a hexyl gamma-butyrolactonewas obtained with a 65% yield based on the tertiary butyl hydroperoxide.

EXAMPLE 58

Acetic acid was reacted in the presence of ceric acetate with4-decyne-1-ene to form gamma-2-octyne butyrolactone. The selectivity ofthe addition of the carboxymethyl radical to the terminal olefinrelative to its addition to the internal acetylenic bond was in excessof 5 to 1.

The gamma-2-octyne butyrolactone was hydrogenated at atmosphericpressure over palladium deposited on carbon to produce gamma-2-octenebutyrolactone. The latter product, synthesized as described, is amammalian pheromone identified and determined by others from studies ofthe male tarsal scent in black-tailed deer.

Gamma-butyrolactones are well known compounds and have various knownuses. Thus, the gamma-butyrolactone produced by the process of theinvention from acetic or propionic acid and cyclohexene may be employedas agents against animal parasites, for example, as anthelmintics; andas agents for destroying noxious pests (U.S. Pat. No. 2,007,813). Thegamma-butyrolactone produced by the process of the invention fromcyanoacetic acid and ethylene may be employed as an insecticide orlarvacide providing protection to articles commonly infested such asagricultural products, weaving apparel and the like (U.S. Pat. No.2,362,614). The gamma-butyrolactones produced by the process of theinvention from propionic acid and isobutene, acetic acid and (HOOC--CH₂--CH₂)C(CH₃)═CH₂, and HOOC--(CH₂)₃ --CH(CH₃)--COOH, and isobutene can beused in perfumery and for masking odors in many kinds of compositions;as chemical intermediates, reacting with alcohols to form esters, withammonia, amines and other bases, halogen acids, etc.; and as softenersand plasticizers for polymeric material such as polyvinyl chloride (U.S.Pat. No. 2,839,538). The gamma-butyrolactone produced by the process ofthe invention from glycollic acid and ethylene exhibits activity as aninhibitor of gastric secretion (U.S. Pat. No. 2,995,576). Thegamma-butyrolactones produced by the process of the invention fromacetic, propionic and butyric acids and isobutene and 3-ethyl, butene-1are valuable solvents and useful intermediates for the preparation ofpyrrolidones, chloro acids, thio acids and other organic compounds (U.S.Pat. No. 3,004,989). The gamma-butyrolactone produced by the process ofthe invention from acetic acid and ethylene may be used as a solvent forsoftening cellophane, parchment, and the like (U.S. Pat. No. 3,166,574).The gamma-butyrolactone produced by the process of the invention fromsuccinic acid and RRC═CHR where R contains 1 to 90 carbon atoms can beconverted to an amide to produce a component for a hydrocarbonlubricating oil composition (U.S. Pat. No. 3,200,075). Thegamma-butyrolactones produced by the process of the invention fromacetic acid and ethylene and from R₃ R₃ CH--COOH and R₁ R₂ --C═C(R)₃where H is hydrogen, saturated alkyl, unsaturated alkyl, substitutedaryl and unsubstituted aryl may be used to render a polyester orpolyether based polyurethane foam hydrophilic (U.S. Pat. No. 3,413,245).The gamma-butyrolactones produced by the process of the invention fromhalogen acetic acid and ethylene may be used to produceorgano-phosphorus compounds having insecticidal activity (U.S. Pat. No.3,513,175). The gamma-butyrolactones produced by the process of theinvention from propionic acid and 5-methyl, pentene-1 may be employed asa flavoring agent (U.S. Pat. No. 3,530,149). The gamma-butyrolactonesproduced by the process of the invention from RCH₂ COOH and RHC═CHRwhere R is hydrogen or the same or different alkyl group may be used toproduce alkyl alcohol and its alkyl derivatives (U.S. Pat. No.3,692,849). The gamma-butyrolactones produced by the process of theinvention from acetic acid and RCH═CHR where R is hydrogen or an alkyl,aryl, alkaryl, aralkyl, or cycloalkyl group may be used to producealpha-carboxylactones which are useful as chemical intermediates for thepreparation of the corresponding alpha-methylenelactones, these latterhaving known utility as fungicides and antibiotics (U.S. Pat. No.3,697,542).

The process of the invention provides other useful applications whichdeserve mention because the product involved is of particular interestor because it is convertible to another product of special use. In onecase a high molecular weight product having two different functionalgroups may be formed for use as an antioxidant additive for hydrogenlubricants. The antioxidant additives, by addition to the lubricants,prevent oxidative deterioration of the lubricants. A conventional butinconvenient way of making a product of this type is to react a butenepolymer with maleic anhydride and an amine to form a structure of thefollowing type, ##STR37## where C₉₀ - is the butene polymer moiety.According to the invention, a product of this type may be prepared byreacting a polymer of a four carbon atom olefin, i.e., butene orisobutene, containing about 90 carbon atoms and having terminalunsaturation with manganic acetate to form the lactone, then reactingthis with an amine, RHN₂, to form products like ##STR38## By furthertreatment of (L) with an amine, RNH₂, there may be formed ##STR39## (N).Compounds (M) and (N) are useful as antioxidant additives. Secondaryamines can replace the RNH₂.

In another case, antioxidant additives for light hydrocarbondistillates, to prevent oxidative deterioration thereof, may be preparedby reacting propylene tetramer, a terminally unsaturated C12hydrocarbon, with manganic acetate to form ##STR40## which on treatmentwith RNH₂ gives the following imide, ##STR41## useful for antioxidantuse.

An improved adherence in the wax coating of paper can be obtained bytaking a C20 to C22 terminal olefin, converting it to a lactone in themanner described, mixing the lactone with the wax, and using the mixturefor coating paper by hot melt technique.

The lactone formed from acetic acid and butadiene, ##STR42## may bereacted either with a polyamine like hexamethylene diamine, or with anacrylate polymer, to form in either case a polymer product for use as anon-metallic detergent in gasoline and other hydrocarbon fractions. Thereaction with acrylate polymer involves copolymerization of thecarbon-to-carbon double bond of the lactone.

The lactone made from acetic acid and styrene, note Example 7, can beused in the single step sodium acetate fusion reaction to producealpha-naphthol, a useful intermediate, particularly for makinginsecticides.

With a polychloroethylene as the unsaturated compound, the resultinglactone is useful to make flame-retarding compounds.

The lactone formed from acetic acid and butene-1, having the formula##STR43## when treated with hot strong acid like polyphosphoric acid, isconvertible to cyclohexenone. Similarly, other lactones derived fromstraight chain 1-olefins may be converted to cycloalkenones, includingcyclopentenones and cyclohexenones using polyphosphoric acid, or zincchloride in acetic acid or acetic anhydride, or stannic chloride ineither acetic acid or acetic anhydride.

The lactone from oleic acid and ethylene, i.e.,beta-carboxyheptyl-gamma-octyl-butyrolactone may be hydrolyzed with acidto produce 9-carboxymethyl-10-hydroxy-octadecanoic acid, a longdicarboxylic acid having a gamma hydroxy group, which can be used in themanufacture of alkyd resins by condensation with a polyhydric alcohol.Similar products are obtainable, starting with abietic acid, the mainconstituent of rosin. Of further interest is the capability of thelactone from oleic acid to undergo self-esterification.

Lactones from acetic acid and propylene and butylene are solvents of the"cellosolve" type, i.e., able to dissolve various cellulose derivatives.Lactones from acetic acid and an olefin like decene are useful aslubricant additives to prevent corrosion of ferrous metals.

Starting with heptene-1, one can make the lactone, as described, thenhydrogenate it to form n-nonanoic acid, a saturated straight chainmonocarboxylic acid, with the carboxyl group on a terminal carbon atom,useful for making jet engine lubricants. In this way, saturated straightchain normal C7, C8, C10, and C11 acids may be made, all of which may beemployed to make jet oils and lubricants. Mixtures of these olefins maybe used to make mixtures of the acids.

The lactone from acetic acid and heptene-1 can also be hydrogenated overa catalyst like copper chromite to yield a 1,4-diol. Thus, ##STR44## Theproduct is 1,4-dihydroxynonane. Diols of this kind are of use to makepolyesters by condensing them with dibasic acids. Lactones from C3 toC20, C30 or higher olefins may be converted in the foregoing way.

Glutaric acid is obtainable by hydrogenating the lactone from aceticacid and acrylic acid, ##STR45## to give the compound, COOHCH₂ CH₂ CH₂COOH. Lactones from other unsaturated monocarboxylic acids, such ascrotonic, also give dicarboxylic acids, which are valuable for polyamideresin formation through condensation with diamines. A dicarboxylic acidmay also be formed starting with butadiene, which is converted to adilactone, ##STR46## and then hydrogenated to ##STR47## Other conjugateddiolefins lead to dicarboxylic acids.

What is claimed is:
 1. A method for the production of agamma-butyrolactone having the structure ##STR48## wherein --X₁ and --X₂are substituents individually selected from the group consisting of--Cl, --Br, --CN, --COCH₃, and COOAlk wherein Alk is an alkyl group withup to six carbon atoms, and --X₃ is selected from the group consistingof hydrogen, --CH₃, --C₂ H₅, --CN and --COOH, which comprises: reacting,under reaction conditions, a diene having the structure ##STR49##wherein --X₁ and --X₂ are as hereinabove described, with a carboxylicacid having the structure ##STR50## wherein --X₃ is as hereinabovedescribed, in the presence of a stoichiometric amount of tetravalentcerium or trivalent manganese salt; and recovering saidgamma-butyrolactone.
 2. The method described in claim 1 wherein --X₃ ishydrogen and the reaction is conducted in the presence of astoichiometric amount of trivalent manganese salt.
 3. The methoddescribed in claim 2 wherein both --X₁ and --X₂ are --Cl.
 4. The methoddescribed in claim 2 wherein --X₁ is --COOCH₃ or --COOC₂ H₅ and --X₂ is--CH₃.
 5. The method described in claim 2 wherein --X₁ is --COCH₃ and--X₂ is --CH₃.
 6. The method described in claim 2 wherein both --X₁ and--X₃ are --Br.
 7. The method described in claim 2 wherein --X₁ is --CNand --X₂ is --CH₃.
 8. The method described in claim 2 wherein --X₁ is--COOCH₃ or --COOC₂ H₅ and --X₂ is --COCH₃.
 9. The method described inclaim 2 wherein both --X₁ and --X₂ are --CN.
 10. The method described inclaim 2 wherein --X₁ is --COOCH₃ or --COOCH₂ H₅ and --X₂ is --Cl or--Br.